Adsorption mode of the chiral modifier cinchonidine on Au(1 1 1)

The adsorption of the chiral modifier cinchonidine on Au(l 1 1) in UHV has been studied by means of TPD, LEED and XPS. In the monolayer the molecule is bound via nitrogen lone pair electrons of its quinoline part rather than via the π-system of this aromatic moiety. Intact molecular desorption is only observed for the multilayers. Decomposition in the first monolayer upon heating occurs above 400 K, indicating a stronger interaction in the monolayer. No long-range ordered structures were observed via LEED. Long-time exposure leads to rearrangement and further stabilization of the first molecular monolayer. Quinoline is bound to gold via the nitrogen lone pair as well. The binding energy of 9.6 kcal/mol is characteristic for physisorption.     

Supercritical carbon dioxide: an inert solvent for catalytic hydrogenation?

Various surface species originating from the reaction between CO2 and H2 over Al2O3-supported Pt, Pd, Rh, and Ru model catalysts were investigated by attenuated total reflection infrared (ATR-IR) spectroscopy under high-pressure conditions. Two different spectroscopic cells were used: a variable-volume view cell equipped with ATR-crystal and transmission IR windows (batch reactor) and a continuous-flow cell also equipped with a reflection element for ATR-IR spectroscopy. The study corroborated that CO formation from dense CO2 in the presence of hydrogen occurs over all Pt-group metals commonly used in heterogeneous catalytic hydrogenations in supercritical CO2 (scCO2). In the batch reactor cell, formation of CO was detected on all metals at 50 and 90 degrees C, with the highest rate on Pt. Additional surface species were observed on Pt/Al2O3 at 150 bar under static conditions. It seems that further reaction of CO with hydrogen is facilitated by the higher surface concentration at higher pressure. In the continuous-flow cell, CO coverage on Pt/Al2O3 was less prominent than that in the batch reactor cell. A transient experiment in the continuous-flow cell additionally revealed CO formation on Pt/Al2O3 at 120 bar after switching the feed from a H2-ethane to a H2-CO2 mixture. The in situ ATR-IR measurements indicate that CO formation in CO2-H2 mixtures is normally a minor side reaction during hydrogenation reactions on Pt-group metal catalysts, and dense ("supercritical") CO2 may be considered as a relatively "inert" solvent in many practical applications. However, blocking of specific sites on the metal surface by CO and consecutive products can affect structure sensitive hydrogenation reactions and may be at the origin of unexpected shifts in the product distribution.     

A combinatorial characterization of quadrics

In this paper we prove that in a projective space of dimension three and orderq the two plane characterk-sets fork {q ²+ 1,(q+1)²} are of the same type as the elliptic or the hyperbolic quadric, respectively. As a corollary we obtain a characterization of the elliptic and the hyperbolic quadrics.     

Molecular reorientational dynamics of d-camphor systems under high pressure

The molecular dynamics of the plastic phase of d-camphor and d-camphor in n-hexane were probed using Raman spectroscopy. The orientational correlation functions of the various systems were found to decay at equal rates in the short time. In the time domain 0 to 1.5 ps the molecular reorientation of d-camphor molecules in n-hexane solution seems to be unaffected by pressures up to 5 kbar.     

Structural characterization of complexes between iminodiacetate blocked on styrene-divinylbenzene matrix (Chelex 100 resin) and Fe(III), Cr(III), and Zn(II) in solid phase by energy-dispersive X-ray diffraction.

Local structure of Fe(III), Cr(III), and Zn(II) cations has been determined on the amorphous sample by means of the difference method used for liquid systems. We recorded energy-dispersive X-ray diffraction spectra of a chelating resin (Chelex 100), containing paired iminodiacetate ions coupled to a styrene-divinylbenzene support, in several ionic forms. Coordination geometry of Fe(III), Cr(III), and Zn(II) metal cations with Chelex 100 resin ligand sites, and conformation of the ligand groups have been determined.     

A comparison of extensional viscosity measurements from various RME rheometers

The transient uniaxial extensional viscosity η _e of linear low density polyethylene (LLDPE) has been measured using the commercial Rheometric Scientific RME and the Münstedt Tensile Rheometer in an effort to compare the performance of available extensional rheometers. The RME indicated a significant strain hardening of the LLDPE, especially at a strain rate of 1 s⁻¹. In contrast, the Münstedt rheometer showed the LLDPE to be only slightly strain hardening. This artificial strain hardening effect in the RME resulted from the strain rate applied to the sample, determined from the sample deformation, being up to 20% less than the set strain rate. These results initiated a round-robin experiment in which the same LLDPE was tested on several RMEs in various locations around the world. All but one of the RMEs indicated a deviation between set and applied strain rates of at least 10%, especially at strain rates above 0.1 s⁻¹. The strain rate deviation was found to depend strongly on the value of the basis length L ₀ , and may result from the upper pair of belts not properly gripping the sample during extension. Thus visual inspection of the sample deformation is necessary to determine the applied strain rate. The most accurate measurements of η _e with respect to the strain rate deviation were obtained when the correct L ₀ value and belt arrangement were used. A list of recommendations for running an RME test is provided. Future work focusing on the fluid mechanics during the test may identify fully the cause of the strain rate deviation, but from a practical point of view the problem can be corrected for in the determination of η _e . Received: 27 September 2000/Accepted: 5 February 2001     

α‐Haloketal (1′R,4S,5S)‐dimethyl 2‐(1′‐bromoethyl)‐2‐(3,4‐dimethoxyphenyl)‐1,3‐dioxolane‐4,5‐dicarboxylate

The crystal structure and absolute configuration of the title compound, C₁₇H₂₁BrO₈, have been determined by X‐ray analysis. They confirmed the 1′R absolute configuration at the 1′‐bromoethyl moiety which has been assigned previously on the basis of chemical and spectroscopic data. Cohesion of the crystal can be attributed to weak intermolecular C—H?O and van der Waals interactions.     

Removal of Methylene Blue from Aging Water Solutions Treated by a Submerged Arc

Low voltage, low energy submerged pulsed arcs with a pulse repetition rate of 100 Hz, energies of 2.6–192 mJ and durations of 10–40 μs, followed by aging in the dark, were used to decompose 10 mg/l methylene blue (MB) dissolved in 40 ml of water, with the addition of 0.5 % H₂O₂. Electrode pairs composed of Fe/Fe, Ti/Ti, Cu/Cu, Cu/Fe, Fe/Cu, Ti/Fe, Fe/Ti, Cu/Ti and Ti/Cu were used. MB degraded during arc treatment, and during post arc treatment aging. The aging degraded MB faster (by a factor of ~2–3) when the MB solution was subjected to arcing with dissimilar electrodes when one of them was Cu, than for arcing with other used electrode pairs. The impact of the arc treatment time and the electrode materials on the MB removal ratio (C₀–C_ta)/C₀ was determined as a function of aging time t_a, where C₀ and C_ta are the MB concentrations initially and after t_a. For a pulse duration of 10 μs and pulse energies of 2–20 mJ, the MB removal rate increased linearly with treatment time and its growth rate increased with pulse energy. The linear dependence of the MB removal rate on treatment time was violated with pulse duration of 40 μs and pulse energies of 30–200 mJ. Kinetics of the MB degradation during aging of the arc treated solution was well described by the 1st order linear rate equation.